Although behavioral and neuropsychological studies have suggested two distinct routes of phonological access, their neural substrates have not been clearly elucidated. Here, we designed an artificial language (based on Korean Hangul) that can be read either through addressed (i.e., whole word mapping) or assembled (i.e., grapheme-to-phoneme mapping) phonology. Two matched groups of native English-speaking participants were trained in one of the two conditions, one hour per day for eight days. Behavioral results showed that both groups correctly named more than 90% of the trained words after training. At the neural level, we found a clear dissociation of the neural pathways for addressed and assembled phonologies: There was greater involvement of the anterior cingulate cortex, posterior cingulate cortex, right orbital frontal cortex, angular gyrus and middle temporal gyrus for addressed phonology, but stronger activation in the left precentral gyrus/inferior frontal gyrus and supramarginal gyrus for assembled phonology. Furthermore, we found evidence supporting the strategy-shift hypothesis, which postulates that, with practice, reading strategy shifts from assembled to addressed phonology. Specifically, compared to untrained words, trained words in the assembled phonology group showed stronger activation in the addressed phonology network and less activation in the assembled phonology network. Our results provide clear brain-imaging evidence for the dual-route models of reading.